Nonlinear optical materials with reduced aromaticity and bond length alternation

ABSTRACT

Compositions for use in non-linear optical devices. The compositions have high first molecular electronic hyperpolarizability (β) and therefore display high second order non-linear optical properties when incorporated into non-linear optical devices. The acceptor and donor groups which are used in the compositions, along with the π(pi)-bridge length is chosen to optimize second-order non-linear optical responses.

The U.S. Government has certain rights in this invention pursuant toContract No. CHE 9106689, National Science Foundation, and Contract No.AFOSR-ISSA-91-0070 awarded by the United States Air Force/DefenseAdvanced Research Projects Agency.

This is a divisional of copending application Ser. No. 08/372,964 filedon Jan. 17, 1995 now pending which is a continuation-in-part ofapplication Ser. No. 08/103,281 which was filed on Aug. 5, 1993 nowabandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates generally to materials which exhibitnonlinear optical (NLO) properties. More particularly, the presentinvention relates to materials which have high first molecularelectronic hyperpolarizability (β) and therefor display high secondorder nonlinear optical properties.

2. Description of Related Art

Organic materials that show second-order nonlinear optical responses areof interest for a variety of photonic and optoelectronic applications.See Marder, S. R., Sohn, J. E. & Stucky, G. D. eds. Materials forNonlinear Optics: Chemical Perspectives, ACS Symposium Series, Vol.455(American Chemical Society, Washington, 1991); Chemla, D. S. & Zyss,J. eds Nonlinear optical properties of Organic Molecules and Crystals,Vol. 1 and 2 (Academic Press, San Diego, 1987); and Williams, D. J.Agnew. Chem. Int. Ed. Engl. 23, 690-703 (1984).

Exemplary nonlinear optical materials and devices which utilize suchmaterials are described in U.S. Pat. Nos. 5,062,693; 5,011,907; and5,016,063. Nonlinear optical materials are also described in JapanesePatent Appln. No. 63-270834 fried Oct. 28, 1988, and published on May 2,1990.

Compositions which have been investigated for second order nonlinearproperties include barbituric acid derivatives and cyanine dyes.Investigations with respect to barbituric acid derivatives are set forthin a number of literature references. These references include: Chapter12 of Materials for Nonlinear Optics: Chemical Perspectives (supra,pp.200-213); Kondo, K. et al., Nonlinear Optical Properties ofp-Substituted Benzalbarbituric Acids,--Appl. Phys. Lett. 56, 718 (1990);Ikeda H., et al., Second Order Hyperpolarizabilities of Barbituric AcidDerivatives, Chemistry Letters, pp. 1803-1806(1989); and Kondo K., etal., Crystal Structure of Thermally Stable Non-Linear BenzalbarbituricAcid Derivatives, Chemical Physics Letters, Vol. 188, No. 3.4, (1992).Investigations with respect to cyanine dyes are set forth in Ikeda, H.,et al., Nonlinear Optical Properties of Cyanine Dyes, Chemical PhysicsLetters, Vol. 179, No. 5.6(1991).

Nonlinear optical compositions are also disclosed in U.S. Pat. No.5,256,784 which issued on Oct. 26, 1994. The disclosed double functionalgroup compositions include a variety of donor groups which are connectedtogether by linkages composed of from 1 to 2 carbon double bonds.

There is a continuing need to develop new materials which havesufficiently high second-order nonlinear optical properties when used inthin films and crystals to make them useful for applications such astelecommunications, optical data storage and optical informationprocessing.

SUMMARY OF THE INVENTION

The present invention provides compositions of matter that have bondlength alternations which are selected to provide a high degree of firstmolecular electronic hyperpolarizability (β). The compositions of thepresent invention are useful for incorporation into polymers,Langmuir-Blodgett thin films, self-assembled monolayers or poledpolymers. It was discovered in accordance with the present inventionthat molecules that have degenerate or more nearly degenerateπ(pi)-electron bridges and do not lose aromaticity upon charge transfer.This diminishes the bond length alternation for given donor-acceptor endgroups and provides optimization of β. Applicants' invention is furtherbased upon the discovery that there is an optimal combination of donorsand acceptors which leads to an optimal degree of bond lengthalternation and therefore optimized β. In addition, it was discoveredthat when the number of carbon double bonds linking certain donor groupis increased above 2, then an unexpected increase in second-ordernonlinear optical properties is observed.

Compositions in accordance with the present invention have the formula##STR1##

wherein A is ##STR2## R is H, alkyl, aryl, (CH₂)_(x) OH where x=1 to 8,or (CH₂)_(x) SH where x=1 to 8;

R' is H, alkyl, aryl, (CH₂)_(y) OH where y'=1 to 8, or (CH₂)_(y') SHwhere y'=1 to 8; ML_(n) is a lewis acid;

wherein B is ##STR3## D is OR", NR" R"' or SR"; where R" is H, alkyl,aryl or (CH₂)_(w) OH where w=1 to 8;

R"' is H, alkyl, aryl or (CH₂)_(z) OH where z=1 to 8;

or where NR" R"' is derived from a cyclic amine of the form N(CH₂)₁where 1=3-10, and

wherein m is 0 to 15 except, if B is (11), and A is (3), (4), (5), (6),(7), (8), (9) or (10) then, m is 2 to 15;

or if B is (11) and A is (1) or (2), then m=3 to 15

where the asterisk indicates the point of attachment on the acceptor anddonor.

As a feature of the present invention, nonlinear optical devices areprovided which include compositions of matter which exhibit a highsecond-order nonlinear optical response. The compositions used in theoptical devices are those set forth above and also include compositionshaving the formula ##STR4## wherein Z is CH═CH, O, N, S or Se;

A is ##STR5## R is H, alkyl, aryl, (CH₂)_(x) OH where x=1 to 8, or(CH₂)_(x) SH where x=1 to 8;

R' is H, alkyl, aryl, (CH₂)_(y) OH where y'=1 to 8, or (CH₂)_(y) SHwhere y'=1 to 8; ML_(n) is a lewis acid;

wherein B is ##STR6## Y is CH═CH, O, N, S or Se; D is OR", NR" R" or SR"where

R" is H, alkyl, aryl or (CH₂)_(w) OH where w=1 to 8;

R"' is H, alkyl, aryl or (CH₂)_(z) OH where z=1 to 8;

or where NR" R"' is derived from a cyclic amine of the form N(CH₂)₁where 1=3-10, and

wherein m is 0 to 15, n=0 to 15 and p=1 to 15; except when A is (2) thenY is S, and B is (13) or (14), M=0 to 10, n=0 to 15 and p=1 to 15,

where the asterisk indicates the point of attachment on the acceptor anddonor.

Further compositions in accordance with the present invention includethose having the formula ##STR7##

wherein C is ##STR8##

wherein A is ##STR9## R is H, alkyl, aryl, (CH₂)_(x) OH where x=1 to 8,or (CH₂)_(x) SH where x=1 to 8;

R' is H, alkyl, aryl, (CH₂)_(y') OH where y'=1 to 8, or (CH₂)_(y') SHwhere y'=1 to 8; ML_(n) is a lewis acid;

wherein B is ##STR10## Y is CH═CH, O, NH, S or Se; D is OR", NR" R"' orSR" where

R" is H, alkyl, aryl or (CH₂)_(w) OH where w=1 to 8;

R"' is H, alkyl, aryl or (CH₂)_(x) OH where z=1 to 8;

or where R" R"' is derived from a cyclic amine of the form N(CH₂)₁ where1=3-10; and

wherein m is 0 to 15.

where the asterisk indicates the point of attachment on the acceptor anddonor.

Applicants' invention focuses on the importance of the conjugatedπ(pi)-electron bridge in determining second-order non-linear opticalresponses. As a feature of the present invention, it was discovered thatthe aromaticity of the bridge in the ground state is an important aspectin determining the degree of bond length alternation and resultantsecond-order nonlinear optical responses. This is in contrast toprevious teachings which typically focused on the aromaticity ofmolecules on either side of the π(pi) electron bridge. The previousteachings focused on optimizing β by changing the strength of the donorand acceptor moieties (i.e. A and B) with the philosophy being thatlarge 11 is obtained by using the strongest donors and acceptors.

The above-discussed and many other features and attendant advantageswill become better understood by reference to the following detaileddescription when taken in conjunction with the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic representation of the synthesis of an exemplarycomposition in accordance with the present invention wherein B isdimethylaminophenyl (11).

FIG. 2 is a schematic representation of the synthesis of an exemplarycomposition wherein B is julolidinyl (12).

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

The compositions of the present invention are organic materials thatshow second-order non-linear optical responses. The compositions areincorporated into thin films and crystals in the same manner as othermaterials which exhibit non-linear optical properties. The compositions,themselves, may exist as crystals, liquids or gases. The compositionsmay be used alone or in combination with other materials which areconventionally used in non-linear optical devices.

The optical element in accordance with the invention may in some casesconsist of a macroscopic crystal of the compound chosen, providing thecompound can be made to form crystals in which the polar molecules arein noncentrosymmetric alignment. Such crystals may be grown at a slowrate under equilibrium with their mother liquor by a variety of methodspracticed in the art. However, this procedure will not work for manypolar molecules due in large part to dipole interactions. Another methodof producing a useful optical element involves dissolving the compoundin a solvent, which can be placed in a container having the desiredshape. The solution can then be subjected to an electrical field whichcauses the dissolved dipoles to align themselves in the field.Electromagnetic radiation can then be passed through the solution andnonlinear optical effects, such as second harmonic generation, can beproduced. Both the presence of an electric field and the need to utilizethe compound in liquid solution form may be inconvenient or undesirablein some applications.

A particularly convenient and effective form of the optical element inaccordance with the invention involves dispersing the polar molecules ina polymeric binder. The polar molecules can be mixed into the polymericbinder or grated onto the polymer. The mixture can be heated to atemperature at which the polymer becomes sufficiently soft so that uponapplication of an electrical field the polar molecules line up on thedirection of the field. When the mixture cools, the polar molecules arelocked into their aligned positions after which the electrode field canbe removed. Suitable binders include polymethacrylate, poly(methylmethacrylate), poly(vinyl alcohol), copolymers of methyl methacrylateand methacrylic acid, copolymers of styrene and maleic anhydride andhalf ester-acids of the latter, as well as many others. It is preferredthat the polymeric binder of choice be highly transparent so that thetransparency of the compounds utilized in the practice of this inventioncan be advantageously employed.

The poled polymer of this invention are considered particularly usefulbecause of their high concentration of nonlinear optically activemolecules, their capability of being formed into large area thin films,and their high orientational stability. Preferred film thickness canvary according to use. Typically film thickness is within the range of0.5 μm-2 μm.

The poled polymer can also be provided in forms other than films (e.g.,a solid block of polymer could be formed into an electrooptic modulatoror a frequency converter using conventional techniques known in the artfor single crystals) and poled polymer in various forms are includedwithin this invention.

The poled polymers of this invention are preferably shaped to functionas nonlinear optical elements for transforming electromagnetic radiation(e.g., by changing the frequency and/or polarization of the radiation).Generally, the nonlinear optical element of a poled polymer is used fortransforming electromagnetic radiation by including it within an opticaldevice. A device for transforming electromagnetic radiation using anonlinear optical element is described in U.S. Pat. No. 4,909,964. Thecompounds of the present invention may be used in such a device.

A conventional nonlinear optical device disclosed in U.S. Pat. No.4,909,964 comprises means to direct at least one incident beam ofelectromagnetic radiation into an element. The element has nonlinearoptical properties whereby electromagnetic radiation emerging from theelement contains at least one frequency different from the frequency ofany incident beam of radiation. The different frequency is an evenmultiple of the frequency of one incident beam of electromagneticradiation.

Preferably, the emerging radiation of a different frequency is doubled(second-order) (SHG). Preferably, the electromagnetic radiation isradiation from one of a number of common lasers, such as Nd-YAG,Raman-shifted Nd-YAG, Nd-YLF or Nd-glass, semiconductor diode, Er-Glass,Ti-Sapphire, dye, and Ar or Kr ion, or radiation shifted to otherfrequencies by nonlinear processes. For example, polarized light ofwavelength 1.06 μm from an Nd-YAG laser is incident on the opticalelement along the optical path. A lens focuses the light into theoptical element. Light emerging from the optical element is collimatedby a similar lens and passed through a filter adapted to remove light ofwavelength 1.06 μm while passing light of wavelength 0.53 μm.

As disclosed in U.S. Pat. No. 4,909,964 (incorporated herein byreference), one conventional electro-optic modulator comprises means todirect a coherent beam into an optical element, and means to apply anelectric field ot the element in a direction to modify the transmissionproperty of the beam. For example, in an electro-optic modulatorcomprising an optical element, a pair of electrodes is attached to theupper and lower surfaces of the element, across which a modulatingelectric field is applied from a conventional voltage source. Theoptical element is placed between two polarizers. A light beam (such asthat from a Nd-YAG laser) is polarized by a polarizer, focused on theoptical element and propagated therethrough, and subjected to modulationby the electric field. The modulate light beam is led out through ananalyzer polarizer. Linearly polarized light traversing the opticalelement is rendered elliptically polarized by action of the appliedmodulating voltage. The analyzer polarizer renders the polarizationlinear again. Application of the modulating voltage alters thebirefringence of the optical element and consequently the ellipticityimpressed on the beam. The analyzer polarizer then passes a greater orlesser fraction of the light beam as more or less of the ellipticallypolarized light projects onto its nonblocking polarization direction.

It will be further apparent to those skilled in the art that the opticalelements formed by the poled polymers of the present invention areuseful in this and other devices utilizing their nonlinear properties,such as devices utilizing the electro-optic effect.

One common form the optical element can take is that of aLangmuir-Blodgett (LB) film. A small amount of a compound useful in thepractice of this invention spread on the surface of a liquid forms asurface film of monomolecular thickness at the air/liquid interface. Ifthe supporting liquid is a polar liquid, such as water, the hydrophilicmoieties of the compound are drawn into the liquid, while thehydrophobic moieties of the compound are attracted to the non-polar, airside of the interface to hold the polar molecules at the surface of thesupporting liquid body, resulting in polar alignment of the polarmolecules on the surface of the supporting liquid. When the supportingsubstrate is slowly immersed in the film bearing liquid body or slowlywithdrawn from it, an oriented monomolecular film is formed on thesubstrate.

The nonlinear optical device according to the invention comprises ameans to direct at least one incident of electromagnetic radiation ontoan optical element having nonlinear optical properties wherebyelectromagnetic radiation emerging from the element contains at leastone frequency different from the frequency of any incident beam ofradiation, the different frequency being an even multiple of thefrequency of one incident beam of electromagnetic radiation. The opticalelement is selected from one of the forms described above. Preferably,the emerging radiation of a different frequency is doubled, i.e. SHG.

The optical element of the invention can also be utilized in anelectro-optic modulator, wherein an electric field is applied to theoptical element in a direction to modify the transmission properties ofthe element.

Compositions of matter which are covered by the present invention havethe formula: ##STR11##

wherein A is ##STR12## R is H, alkyl, aryl, (CH₂)_(x) OH where x=1 to 8,or (CH₂)_(x) SH where x=1 to 8;

R' is H, alkyl, aryl, (CH₂)_(y') OH where y'=1 to 8, or (CH₂)_(y') SHwhere y'=1 to 8; n is 0 to 10 and ML_(n) is a lewis acid;

wherein B is ##STR13## D is OR", NR" R"' or SR" where R" is H, alkyl,aryl or (CH₂)_(w) OH where w=1 to 8;

R"' is H, alkyl, aryl or (CH₂)_(z) OH where z=1 to 8;

or where NR" R"' is derived from a cyclic amine of the form N(CH₂)₁where 1=3-10, and

wherein m is 0 to 15 except, if B is (11) and A is (3), (4), (5) (6),(7), (8), (9) and (10), then m is 2 to 15;

or if B is (12) and A is (1), then m is 1 to 15;

or if B is (11) and A is (1) or (2), then m=3 to 15;

where the asterisk indicates the point of attachment on the acceptor anddonor.

The present invention is also directed to non-linear optical deviceswhich incorporate compositions of matter having the formula: ##STR14##wherein Z is CH═CH, O, N, S or Se;

A is ##STR15## R is H, alkyl, aryl, (CH₂)_(x) OH where x=1 to 8, or(CH₂)_(x) SH where x=1 to 8;

R' is H, alkyl, aryl, (CH₂)_(y') OH where y'=1 to 8, or (CH₂)_(y') SHwhere y'=1 to 8; ML_(n) is a lewis acid;

where the asterisk indicates the point of attachment on the acceptor anddonor.

wherein B is ##STR16## Y is CH═CH, O, N, S or Se; D is OR", NR" R"' orSR" where

R" is H, alkyl, aryl or (CH₂)_(w) OH where w=1 to 8;

R"' is H, alkyl, aryl or (CH₂)_(x) OH where z=1 to 8;

or where NR" R"' is derived from a cyclic amine of the form N(CH₂)₁where 1=3-10, and

wherein m is 0 to 15, n =0 to 15 and p=1 to 15; except when A is (2)then Y is S, and B is (13) or (14), m=0 to 10, n=0 to 15 and p=15 to 15,

where the asterisk indicates the point of attachment on the acceptor anddonor.

The present invention is also directed to non-linear optical deviceswhich include compositions of matter having the formula: ##STR17##

wherein C is ##STR18##

wherein A is ##STR19## R is H, alkyl, aryl, (CH₂)_(x) OH where x=1 to 8,or (CH₂)_(x) SH where x=1 to 8;

R' is H, alkyl, aryl, (CH₂)_(y') OH where y'=1 to 8, or (CH₂)_(y') SHwhere y'=1 to 8; ML_(n) is a lewis acid;

wherein B is ##STR20## Y is CH═CH, O, N, S or Se; D is OR", NR" R"' orSR" where

R" is H, alkyl, aryl or (CH₂)_(w) OH where w=1 to 8;

R"' is H, alkyl, aryl or (CH₂)_(z) OH where z=1 to 8;

or where R" R"' is derived from a cyclic amine of the form N(CH₂)₁ where1=3-10, and

wherein m is 0 to 15.

where the asterisk indicates the point of attachment on the acceptor anddonor.

Alkyl groups set forth in the above formulas include those groups havingup to 10 carbon atoms and includes both branched and straight chainalkyl groups. Exemplary alkyl groups include methyl, ethyl, propyl,butyl, pentyl, hexyl, heptyl, octyl, nonyl, in the normal, secondary,iso and neo attachment isomers. Aryl groups referred to in the precedingformulas include aromatic hydrocarbons having up to 10 carbon atoms.Exemplary aryl groups include phenyl, naphthyl, furanyl, thiophenyl,pyrrolyl, selenophenyl, tellurophenyl. The abbreviation ML_(n) refer toLewis acids. Exemplary Lewis acids include (CH₃)₂ Zn, (CH₃)₃ Al, (CH₃)₃Ga, (CH₃)₃ B Cl₃ Al, Cl₃ Ga, and Cl₃ B.

The compositions of the present invention are prepared by reacting anappropriate acceptor (A) with B--(CH═CH)_(n) CHO under standardKnoevenagel conditions. As schematically shown in FIG. 1 for theexemplary case where B is dimethylaminophenyl (11). FIG. 2 is aschematic representation of the is julolidinyl (12).

A compound in accordance with the present invention was prepared where Awas diethylthiobarbituric acid (2) and B was dimethylaminophenyl (11).The procedure which was used to prepare this composition was as follows:

Preparation of the product is carried out by a conventional Knoevenagelreaction wherein (7-4-dimethylamino-phenyl)-hepta-2, 4, 6-triene-1-al(1.41 mmol) is completely dissolved in approximately 100 mls of ethanol.10 mls of a warm ethanol solution of 1, 3-diethyl thiobarbituric acid(1.11 mmol is added to the dissolved (7-4-dimethylamino-phenyl)-hepta-2,4, 6-triene-1-al. This causes a gradual darkening of color. The mixtureis then set in an oil bath at 90° C. and 0.5 mls of piperidine is addedwith stirring. The color of the solution immediately darkens. Thesolution is then refluxed generally for one hour or until thin layerchromatography (TLC) indicates the reaction is complete. The mixture iscooled and diluted with petroleum ether and the product is filtered andwashed with ethanol/petroleum ether and then with petroleum ether. Theyield is 0.435 gram (1.06 mmol, 95%) of dark green fluffy powder. Thepowder may be recrystallized from mixtures of dichloromethane/petroleumether or from ethanol/petroleum ether. In an alternate procedure, the(7-4-dimethylamino-phenyl)-hepta-2, 4, 6-triene-1-al is combined in 10mls of ethanol and 30 mls of chloroform with 1.0 gram ofisophorone-thiobarbituric acid derivative C, where A=(2) and R═R'═ethyl(3.12 mmol and 1 g ammonium acetate) in a Schlenk flask. The flask isfilled with argon twice and sealed. The mixture is then evacuated andleft to sit one day at room temperature in the dark. The resulting darkblue solution is washed with water (2×30 mls) followed by drying withmagnesium sulfate. Solvent is removed from the solution under vacuum.The remaining residue is chromatographed on silica gel using 3% ethylacetate/97% hexane as an eluant. The first blue band gave afterevaporation of solvent a materials corresponding to a composition havingthe formula of the present invention where A is 2 R═R' is ethyl, C is 16and m is 4 and B is (14), where Y is CH═CH and D is (CH₃)₂ N.

A number of exemplary compositions in accordance with the presentinvention were prepared following the above-described procedure. Theresults of spectroscopic and elemental analysis for the variouscompositions are as follows:

EXAMPLE 1 General Formula I

A=diethyl barbituric acid (1)

B=dimethylaminophenyl (11)

m=3

¹ H NMR (CD₃ COCD₃) δ 7.98 (m, 2H), 7.43 (dm, J=8.8 Hz, 2H), 7.39 (m,1H), 7.04 (dd, J=14.3, 10.5 Hz, 1H), 6.93 (m, 2H), 6 dd, J=14.2, 11.8Hz, 1H), 3.93, 3.92 (each q, J=7.0 Hz, 2H), 3.01 (s, 6H), 1.16, 1.15(each t, J=7.0 Hz, 3H). Anal. Calcd. for C₂₃ H₂₇ N₃ O₃ : C, 70.21; H,6.92; N, 10.68. Found: C, 70.26; H, 6.95; N, 10.67. λ_(max) (solvent,nanometers): cyclohexane, toluene, 546; chloroform, 572; methylenechloride, 562; acetone, 542; methanol, 560; N-methyl-2-pyrrolidone, 569.

EXAMPLE 2 General Formula I

A=diethyl barbituric acid (1)

B=julolidinyl (12)

m=1

¹ H NMR (CD₃ COCD₃) δ 8.36 (dd, J=14.8, 12.4 Hz, 1H), 8.05 (dd, J=12.5,0.6 Hz, 1H), 7.44 (d, J=14.8 Hz, 1H), 7.20 (s, 2H), 3.94, 3.92 (each q,J=7.0 Hz, 2H), 3.37 (apparent t, J=5.8 Hz, 4H), 2.76 (apparent t, J=6.3Hz, 4H), 1.95 (m, 4H), 1.17, 1.15 (each t, J=7.0 Hz, 3H). ¹³ C NMR δ162.77, 162.24, 158.30, 157.87, 151.04, 147.13, 130.05, 122.55, 121.25,119.58, 108.62, 50.19, 36.87, 36.28, 27.48, 21.20, 13.48, 13.43. λ_(max)(solvent, nanometers): cyclohexane, 529; chloroform, 574. Anal. Calcd.for C₂₃ H₂₇ N₃ O₃ : N, 10.68. Found: N, 10.64.

EXAMPLE 3 General Formula I

A=diethyl barbituric acid (1)

B=julolidinyl (12)

m=2

¹ H NMR (CD₂ Cl₂) δ 8.04 (d, J=12.5 Hz, 1H) 7.94 (dd, J=13.9, 12.6 Hz,1H), 7.28 (apparent ddd, J=13.9, 7.9, 2.9 Hz, 1H), 6.99 (s, 2H), 6.92(m, H), 3.96, 3.96 (each q, J=7.0 Hz, 2H), 3.27 (apparent t, J=5.8 Hz,4H), 2.73 (apparent t, J=6.3 Hz, 4H), 1.94 (m, 4H), 1.19 (m, 6H).λ_(max) (solvent, nanometers): cyclohexane, 540; chloroform, 616.

EXAMPLE 4 General Formula I

A=diethylthio barbituric acid (2)

B=dimethylaminophenyl (11)

m=3

¹ H NMR δ 8.09 (d, J=12.6 Hz, 1H), 8.00 (apparent t, J=13.3 Hz, 1H),7.39 (d, J=9.0 Hz, 2H), 7.25 (dd, J=14.0, 11.7 Hz, 1H), 6.96 (dd,J=14.4, 10.2 Hz, 1H), 6.85 (d, J=15.1 Hz, 1H), 6.81 (d, J=15.1, 10.2 Hz,1H), 6.67 (d, J=9.0 Hz, 2H), 6.59 (dd, J=14.3, 11.7 Hz, 1H), 4.55, 4.54(each q, J=7.0 Hz, 2H), 3.04 (s, 6H), 1.30 (m, 6H). ¹³ C NMR δ 178.75,160.87, 159.87, 157.99, 157.27, 151.19, 147.82, 142.07, 130.07, 129.28,128.31, 124.30, 123.92, 112.10, 112.00, 43.58, 43.05, 40.15, 12.42(coincident). Anal. Calcd. for C₂₃ H₂₇ N₃ O₂ S: C, 67.45; H, 6.65; N,10.26. Found: C, 67.48; H, 6.71; N, 10.18. λ_(max) (solvent,nanometers): cyclohexane, 556; toluene, 588; chloroform, 624; methylenechloride, 612; acetone, 592; methanol, 608; N-methyl-2-pyrrolidone, 634.

EXAMPLE 5 General Formula I

A=diethylthio barbituric acid (2)

B=julolidinyl (12)

m=1

¹ H NMR (CD₃ COCD₃) δ 8.40 (dd, J=14.5, 12.7 Hz, 1H), 8.10 (dd, J=12.6,0.5 Hz, 1H), 7.56 (d, J=14.5 Hz, 1H), 7.27 (br s, 2H), 4.52, 4.50 (eachq, J=6.9 Hz, 2H), 3.43 (apparent t, J=5.8 Hz, 4H), 2.78 (apparent t,J=6.5 Hz, 4H), 1.96 (m, 4H), 1.25, 1.22 (each t, J=6.9 Hz, 3H). ¹³ C NMRδ 178.60, 161.37, 160.46, 159.38, 159.18, 147.99, 130.78, 122.74,121.46, 120.11, 108.46, 50.33, 43.41, 42.86, 27.40, 21.04, 12.49, 12.41.Anal. Calcd. for C₂₃ H₂₇ N₃ O₂ S: C, 67.45; H, 6.65; N, 10.26; S, 7.83.Found: C, 67.18; H, 6.67; N, 10.24; S, 7.77. λ_(max) (solvent,nanometers): cyclohexane, 563; chloroform, 614 (log ε, 5.08).

EXAMPLE 6 General Formula I

A=diethylthio barbituric acid (2)

B=julolidinyl (12)

m=2

¹ H NMR δ (CD₂ Cl₂) 8.07 (d, J=12.8 Hz, 1H, 7.98 (apparent t, J=13.2 Hz,1H, 7.37 (dd, J=14, 11.0 Hz, 1H, 7.03 (br s, 2H, 6.98 (m, 2H), 4.54 (m,4H, 3.30 (apparent t, J=5.8 Hz, 4H), 2.73 (apparent t, J=6.3 Hz, 4H,1.95 (m, 4H), 1.27, 1.25 (each t, J=7.0 Hz, 3H). Anal. Calcd. for C₂₅H₂₉ N₃ O₂ S: C, 68.94; H, 6.71; N, 9.65; S, 7.36. Found: C, 69.03; H,6.76; N, 9.63; S, 7.42. λ_(max) (solvent, nanometers): cyclohexane, 580;chloroform, 684.

EXAMPLE 7 General Formula I

A=diethylthio barbituric acid (2)

B=julolidinyl (12)

m=3

¹ H NMR δ 8.08 (d, J-12.7 Hz, 1H), 7.98 (apparent t, J=13.3 Hz, 1H),7.25 (dd, J=13.8, J=11.9 Hz, 1H), 6.96, (bs, 2H), 6.95 (m, 1H), 6.55(dd, J=14.1, J=11.8 Hz, 1H), 4.55, 4.54 (each q, J=6.9 Hz, 2H), 3.25(apparent t, J=5.7 Hz, 4H), 2.74 (apparent t, J=6.3 Hz, 4H), 1.96 (m,4H), 1.31, 1.29 (each t, J=7.3 Hz, 3H). ¹³ C NMR δ 178.05, 161.05,160.04, 157.97, 157.91, 148.80, 144.72, 143.22, 129.39, 127.81, 127.30,123.39, 123.09, 121.28, 111.35, 50.02, 43.58, 43.04, 27.67, 21.53,12.48, 12.44; EIMS, m/z 461(M, 2), 327(47), 199(54), 186(100), 170(32),97(24), 69(34); EI HRMS m/z (calcd for C₂₇ H₃₁ N₃ O₂ S:461.2150),461.2137. Anal. Calcd. for C₂₇ H₃₁ N₃ O₂ S: C, 70.25; H, 6.77; N, 9.10;S, 6.95. Found: C, 70.03; H, 6.80; N, 9.00; S, 6.83.

EXAMPLE 8 General Formula I

A=indandione (3)

B=dimethylaminophenyl (11)

m=2

λ_(max) (solvent, nanometers): toluene, 536; chloroform, 556; methylenechloride, 552; acetone, 542; methanol, 560; N-methyl-2-pyrrolidone, 570.

EXAMPLE 9 General Formula I

A=indandione (3)

B=dimethylaminophenyl (11)

m=3

¹ H NMR δ 7.91 (m, 2H), 7.83 (dd, J=14.3, 12.5 Hz, 1H), 7.73 (m, 2H),7.53 (d, J=8.9 Hz, 2H), 7.37 (dm, J=8.9 Hz, 2H), 7.10 (dd, J=14.5, 11.5Hz, 1H), 6.80 (m, 3H), 6.67 (dm, J=8.9 Hz, 2H), 6.60 (dd, J₁ +J₂ =25.17Hz, 1H), 3.02 (s, 6H). λ_(max) (solvent, nanometers): cyclohexane, 524;toluene, 550; chloroform, 572; methylene chloride, 570; acetone, 552;methanol, 568; N-methyl-2-pyrrolidone, 580.

EXAMPLE 10 General Formula I

A=indandione (3)

B=julolidinyl (12)

m=1

¹ H NMR δ 8.21 (dd, J=14.8, 12.4 Hz, 1H), 7.88, 7.70 (each m, 2H), 7.62(d, J=12.3 Hz, 1H), 7.21 (d, J=14.9 Hz, 1I-I), 7.17 (br. s, 2H), 3.30(apparent t, J=5.7 Hz, 4H), 2.76 (apparent t, J=6.2 Hz, 4H), 1.97 (m,4H). λ_(max) (solvent, nanometers): cyclohexane, 541.

EXAMPLE 11 General Formula I

A=indandione (3)

B=julolidinyl (12)

m=2

¹ H NMR δ 7.89 (m, 2H), 7.82 (dd, J₁ +J₂ =26.75 Hz, 1H), 7.70 (m, 2H),7.54 (d, J=12.6 Hz, 1H), 7.17 (dd, J=14.3, 10.8 Hz, 1H), 6.99 (br. s,2H), 6.92 (dd, J=15.0, 10.7 Hz, 1H), 6.85 (d, J=15.1 Hz, 1H), 3.25(apparent t, J=5.7 Hz, 4H), 2.74 (apparent t, J=6.3 Hz, 4H), 1.97 (m,4H).

EXAMPLE 12 General Formula I

A=3-phenyl-5-isoxazolone (5)

B=dimethylaminophenyl (11)

m=2

¹ H NMR δ (CD₂ Cl₂) 7.81 (dd, J=14.1, 12.3 Hz, 114), 7.57 (m, 5H,), 7.43(d m, J=9.0 Hz, 2H), 7.40 (dd, J=12.6, 0.5 Hz, 1H), 7.18 (apparent dddd,J=14.3, 7.4, 3.3, 0.4 Hz, 1H), 7.00 (m, 2H), 6.69 (d m, J=9.0 Hz, 2H),3.04 (s, 6H); ¹³ C NMR (125.8 MHz) δ 170.21, 162.40, 154.61,151.92,149.73, 145.57, 130.53, 130.02, 129.06, 128.31, 128.24, 124.72, 123.93,123.72, 112.70, 112.09, 40.08; Anal. Calcd. for C₂₂ H₂₀ N₂ O₂ : C,76.72; H, 5.85; N, 8.13. Found: C, 76.67; H, 5.90; N, 8.08. λ_(max)(solvent, nanometers): cyclohexane, 508; toluene, 538; chloroform, 562;methylene chloride, 564; acetone, 553; methanol, 570;N-methyl-2-pyrrolidone, 580.

EXAMPLE 13 General Formula I

A=3-phenyl-5-isoxazolone (5)

B=dimethylaminophenyl (11)

m=3

¹ H NMR δ (CD₂ Cl₂) 7.78 (dd, J=14.3, 12.3 Hz, 1H), 7.58 (m, 5H), 7.37(m, 3H), 7.09 (dd, J=14.4, 11.6Hz, 1H), 6.90 (apparent ddd, J=14.1, 7.0,3.8 Hz, 1H), 6.82 (m, 2H), 6.67 (d m, J=9.0 Hz, 2H), 6.62 (dd, J=13.6,11.6 Hz, 1H), 3.01 (s, 6H, ); ¹³ C NMR (125.8 MHz) δ 170.01, 162.37,153.50, 151.22, 149.35, 146.27, 141.14, 130.59, 129.81, 129.09, 129.07,128.22, 128.17, 125.64, 124.48, 123.97, 113.40, 112.12, 40.15. Anal.Calcd. for C₂₄ H₂₂ N₂ O₂ : C, 77.81; H, 5.99; N, 7.56. Found: C, 77.89;H, 6.02; N, 7.53. λ_(max) solvent, nanometers): cyclohexane, 534;toluene, 558; chloroform, 582; methylene chloride, 578; acetone, 566;methanol, 576; N-methyl-2-pyrrolidone, 592.

EXAMPLE 14 General Formula I

A=3-phenyl-5-isoxazolone (5)

B=julolidinyl (12)

m=0

¹ H NMR (CD₃ COCD₃) δ 8.08 (v br s, 2H), 7.58 (m, 5H), 7.31 (s, 1H),3.46 (apparent t, J=5.8 Hz, 4H), 2.73 (apparent t, J=6.2 Hz, 4H), 1.95(m, 4H); ¹³ C NMR δ 164.85, 150.89, 149.27, 135.55, 135.49, 129.96,128.97, 128.79, 128.73, 121.05, 120.85, 107.03, 50.43, 27.32, 20.82;Anal. Cald. for C₂₂ H₂₀ N₂ O₂ : C, 76.72; H, 5.85; N, 8.13. Found: C,76.82; H, 5.87; N, 8.09. λ_(max) (solvent, nanometers): cyclohexane,476; chloroform, 504.

EXAMPLE 15 General Formula I

A=3-phenyl-5-isoxazolone (5)

B=julolidinyl (12)

m=1

¹ H NMR (CD₃ COCD₃) δ 8.12 (dd J=14.7, 12.2Hz, 1H), 7.66 (m, 2H), 7.61(dd, J=12.2, 0.6 Hz, 1H), 7.56 (m, 3H), 7.42 (d, J=14.6 Hz, 1H), 7.17(s, 2H), 3.38 (apparent t, J=5.8 Hz, 4H), 2.75 (apparent t, J=6.2 Hz,4H), 1.94 (m, 4H). ¹³ C NMR (125.8 MHz) δ 171.10, 162.47, 155.21,150.82, 147.26, 130.16, 129.85, 128.86, 128.72, 128.13, 122.34, 121.37,117.40, 108.89, 50.16, 27.42, 21.10; Anal. Calcd. for C₂₄ H₂₂ N₂ O₂ : C,77.81; H, 5.99; N, 7.56. Found: C, 77.79; H, 6.00; N, 7.49. λ_(max)(solvent, nanometers): cyclohexane, 517; chloroform, 586.

EXAMPLE 16 General Formula I

A=3-phenyl-5-isoxazolone (5)

B=julolidinyl (12)

m=2

¹ H NMR (CD₃ COCD₃) δ 7.75 (dd J=14.1, 12.6 Hz, 1H), 7.66 (m, 2H), 7.58(dd, J=12.6, 0.6 Hz, 1H), 7.57 (m, 3H), 7.42 (dd, J=14.2, J=11.1 Hz,1H), 7.11 (s, 2H), 7.09 (dd J=13.9, 11.0 Hz, 1H), 7.01 (d, J=14.0 Hz,1H), 3.30 (apparent t, J=5.7 Hz, 4H), 2.72 (apparent t, I=6.2 Hz, 4H),1.92 (m, 4H). Anal. Calcd. for C₂₆ H₂₄ N₂ O₂ : C, 78.76; H, 6.10; N,7.07. Found: C, 78.64; H, 6.16; N, 7.05. λ_(max) (solvent, nanometers):cyclohexane, 554; chloroform, 620.

EXAMPLE 17 General Formula I

A=3-phenyl-5-isoxazolone (5)

B=julolidinyl (12)

m=3

¹ H NMR δ 7.79 (dd J=14.1, 12.4 Hz, 1H), 7.59 (m, 2H), 7.52 (m, 3H),7.32 (d, J=12.4 Hz, 1H), 7.04 (dd, J=14.3, J=11.7 Hz, 1H), 6.94 (s, 2H),6.84 (apparent dd J=14.1, 9.8 Hz, 1H), 6.73 (m, 2H), 6.55 (dd J=14.0,11.7 Hz, 1H), 3.24 (apparent t, J=5.7 Hz, 4H), 2.73 (apparent t, J=6.2Hz, 4H), 1.96 (m, 4H). ¹³ C NMR δ 21.51, 27.62, 49.91, 112.12, 121.19,122.91, 123.25, 124.98, 126.97, 128.99, 130.45, 142.20, 144.46, 147.24,149.44, 154.14, 163.06; Anal. Calcd. for C₂₈ H₂₆ N₂ O₂ : C, 79.59; H,6.20; N, 6.63. Found: C, 79.51; H, 6.15; N, 6.61.

EXAMPLE 18 General Formula III

A=diethylthio barbituric acid (2)

B=dimethylaminophenyl (11)

C=isophorone (16)

m=1

¹ H NMR (CD₃ COCD₃) δ 8.38 (s, 1H), 7.59 (dm, J=8.8 Hz, 2H), 7.27 (d,J=15.9 Hz, 1H), 7.06 (dd, J=15.9, 0.5 Hz, 1H), 6.76 (dm, J=9.0 Hz, 2H),4.48 (br, 4H), 3.09 (s, 2H), 3.04 (s, 6H), 2.54 (s, 2H) 1.23 (br m, 6H),1.04 (s, 6H).

EXAMPLE 19 General Formula III

A=diethylthio barbituric acid (2)

B=dimethylaminophenyl (11)

C=isophorone (16)

m=2

¹ H NMR δ 8.32 (s, 1H), 7.37 (dm, J=8.7 Hz, 2H), 6.98 (m, 1H), 6.79 (m,2H), 6.70 (br, 2H), 6.60 (d, J=15.1 Hz, 1H), 4.54, 4.51 (each q, J=6.8Hz, 2H), 3.08 (s, 2H), 3.03 (s, 6H), 2.40 (s, 2H) 1.31, 1.29 (each t,J=6.9 Hz, H), 1.04 (s, 6H).

EXAMPLE 20 General Formula III

A=diethylthio barbituric acid (2)

B=dimethylaminophenyl (11)

C=isophorone (16)

m=3

¹ H NMR δ 8.31 (s, 1H), 7.35 (dm, J=8.6 Hz, 2H), 6.90 (dd, J=15.0,J=11.2, 1H), 6.77 (dd, J=15.2, 10.6 Hz, 1H), 6.70 (br, 2H), 6.68 (dd,J=14.2, 10.7 Hz, 1H), 6.66 (d, J=15.2 Hz, 1H), 6.56 (d, J=15.1 Hz, 1H),6.43 (dd, J=14.1, 11.2 Hz, 1H), 4.55, 4.51 (each q, J=7.0 Hz, 2H), 3.07(s, 2H), 3.01 (s, 6H), 2.38 (s, 2H) 1.31, 1.29 (each t, J=7.0 Hz, 3H),1.04 (s, 6H).

EXAMPLE 21 General Formula III

A=diethylthio barbituric acid (2)

B=dimethylaminophenyl (11)

C=isophorone (16)

m=4

¹ H NMR δ 8.30 (s, 1H), 7.32 (dm, J=8.6 Hz, 2H), 6.87 (dd, J=15.0,J=11.1, 1H, 6.72 (dd, J=15.2, 10.9 Hz, 1H), 6.67 (br d, J=8.0 Hz, 2H,6.61 (dd, J=14.5, 11.3 Hz, 1H, 6.60 (d, J=15.6 Hz, 1H, 6.56 (dd, J=14.4,10.7 Hz, 1H), 6.56 (d, J=15.2 Hz, 1H), 6.39 (dd, J=14.2, 11.5 Hz, 1H,6.39 (dd, J=14.5, 11.2 Hz, 1H, 4.54, 4.51 (each q, J=6.9 Hz, 2H), 3.07(s, 2H), 3.00 (s, 6H), 2.36 (s, 2H) 1.31, 1.29 (each t, I=7.0 Hz, 3H,1.04 (s, 6H).

EXAMPLE 22 General Formula II

A=diethylthiobarbituric acid, (2)

B=(14) with Y=S, D=piperidinyl

m=n=p=0

Anal. Calcd. for C₁₈ H₂₃ N₃ O₂ S₂ : C, 57.27; H, 6.14; N, 11.13; S,16.99. Found: C, 57.10; H 6.20; N, 11.22; S, 16.82. High resolution MScalcd. for C₁₈ H₂₃ N₃ O₂ S₂ : 377.1225. Found: 377.1232.

EXAMPLE 23 General Formula II

A=5-phenyl-3-isoxazolone, (5)

B=(14) with Y=S, D=piperidinyl,

m=1,

n=1, Z=S,

p=0

¹ H NMR (CD₂ Cl₂) δ 7.78 (s, 1H), 7.60 (m, 6H), 7.38 (d, J=15.3 Hz, 1H),7.08 (d, J=4.2 Hz, 1H), 6.98 (d, J=4.2 Hz, 1H), 6.65 (d, J=15.4 Hz, 1H),5.98 (d, J=4.0 Hz, 1H), 3.27 (t, J=5.6 Hz, 4H), 1.71 (m, 4H), 1.62 (m,21H). Anal. Calcd. for C₂₅ H₂₂ N₂ O₂ S₂ : C, 67.24; H, 4.97; N, 6.27; S,14.36. Found: C, 67.26; H, 4.99; N, 6.26; S, 14.29.

EXAMPLE 24 General Formula II

A=diethylthiobarbituric acid, (2)

B=(14) with Y=S, D=piperidinyl,

n=1,

n=1, Z=S,

p=1

¹ H NMR (CD₂ Cl₂) δ 8.28 (dd, J=14.5, 2.2 Hz, 1H), 8.11 (d, J=12.2 Hz,1H), 7.55 (d, J=14.5 Hz, 1H), 7.33 (d, J=4.1 Hz, 1H, ), 7.16 (d, J=15.3Hz, 1H), 6.96 (d, J=4.0 Hz, 1H), 6.90 (d, J=4.1 Hz, 1H), 6.62 (d, J=15.4Hz, 1H), 5.97 (d, J=4.20 Hz, 1H), 4.53 (m, 4H), 3.25 (t, 4H, J=5.7 H1.70 (m, 4H), 1.61 (m, 2H), 1.26 (m, 6H).

Four different compounds produced by the above-described procedure wereanalyzed to determine first molecular hyperpolarizabilities. The resultsof these determinations are set forth in Tables 1-4. Tables 1-3 show themeasured β for the three exemplary compounds in accordance with thepresent invention. Table 4 sets forth measurements for a compound notcovered by the present invention wherein A═CH═CHC₆ H₄ NO₂.

                  TABLE 1                                                         ______________________________________                                        General Formula I                                                             A = CH - diethylthiobarbituric acid (2)                                       B = dimethylaminophenyl (11)                                                                                         μβ/                                                                         μβ(0)/                       # of atoms                                                                             λmax                                                                          μ/10.sup.-18                                                                     β/10.sup.-30                                                                   β(0)/10.sup.-30                                                                 10.sup.-48                                                                          10.sup.-48                       m   conjugated                                                                             (nm)   (esu) (esu) (esu)  (esu) (esu)                            ______________________________________                                        0    9       (484)  5.4    68    48     370   259                             1   11       (572)  5.7   256   150    1457   855                             2   13       (604)  6.2   636   347    3945  2151                             3   15       (624)  6.6   1490  772    9831  5095                             ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                        General Formula I                                                             A = 3 - phenyl-5-isoxazolone (5)                                              B = dimethylaminophenyl (11)                                                                                         μβ/                                                                         μβ(0)/                       # of atoms                                                                             λmax                                                                          μ/10.sup.-18                                                                     β/10.sup.-30                                                                   β(0)/10.sup.-30                                                                 10.sup.-48                                                                          10.sup.-48                       m   conjugated                                                                             (nm)   (esu) (esu) (esu)  (esu) (esu)                            ______________________________________                                        0    9       (478)  8.3    27    56     312   221                             1   11       (530)  8.6   140    90    1202   771                             2   13       (562)  8.7   362   218    3156  1895                             3   15       (582)  8.9   918   528    8171  4696                             ______________________________________                                    

                                      TABLE 3                                     __________________________________________________________________________    General Formula I                                                             A = CHC.sub.6 H.sub.4 NO.sub.2                                                B = dimethylaminophenyl (11)                                                    # of atoms                                                                         λmax                                                                       μ/10.sup.-18                                                                   β/10.sup.-30                                                                  β(0)/10.sup.-30                                                               μβ/10.sup.-48                                                               μβ(0)/10.sup.-48                       m conjugated                                                                         (nm)                                                                              (esu)                                                                             (esu)                                                                              (esu)                                                                              (esu) (esu)                                          __________________________________________________________________________    0 13   (430)                                                                             6.6  73  55   482   363                                            1 15   (442)                                                                             7.6 107  80   813   608                                            2 17   (458)                                                                             8.2 131  95   1074  779                                            3 19   (464)                                                                             9 ± 1                                                                          190 ± 35                                                                        133 ± 35                                                                        1700 ± 400                                                                       1197 ± 250                                  __________________________________________________________________________

                  TABLE 4                                                         ______________________________________                                        General Formula I                                                             A = CH - diethylthiobarbituric acid (2)                                       B = julolidinyl (12)                                                                                                 μβ/                                                                         μβ(0)/                       # of atoms                                                                             λmax                                                                          μ/10.sup.-18                                                                     β/10.sup.-30                                                                   β(0)/10.sup.-30                                                                 10.sup.-48                                                                          10.sup.-48                       m   conjugated                                                                             (nm)   (esu) (esu) (esu)  (esu) (esu)                            ______________________________________                                        0    9       (522)  7.0    87    56     609   394                             1   11       (614)  6.6    355  196    2210  1159                             2   13       (680)  6.3   1141  490    7152  3069                             3   15       (686)  8.8   2169  911    19086 8019                             ______________________________________                                    

As can be seen from the above Tables, compounds in accordance with thepresent invention (Table 1-3) have large first molecularhyperpolarizabilities (β) in comparison with the compound set forth inTable 4. For example, the results in Table 2 show that this exemplarycomposition in accordance with the present invention has a β (0) of911×10⁻³⁰ esu (after correcting for dispersion with a two state model).This is to be compared with the compound in Table 4 which has a β (0) of133×10⁻³⁰ esu. The Tables show that when the number of carbon doublebonds which link the two functional groups together is increased, thefirst hypexpolarizabilities unexpectedly increases.

Having thus described exemplary embodiments of the present invention, itshould be noted by those skilled in the art that the within disclosuresare exemplary only and that various other alternatives, adaptations, andmodifications may be made within the scope of the present invention.Accordingly, the present invention is not limited to the specificembodiments as illustrated herein, but is only limited by the followingclaims.

What is claimed is:
 1. A nonlinear optical device comprising:A) anelement comprising a comprising a composition matter which exhibits asecond-order nonlinear optical response, said composition having theformula: ##STR21## wherein C is ##STR22## wherein A is ##STR23## R is H,alkyl, aryl, (CH₂)_(x) OH where x=1 to 8, or (CH₂)_(x) SH where x=1 to8;R' is H, alkyl, aryl, (CH₂)_(y') OH where y'=1 to 8, or (CH₂)_(y') SHwhere y'=1 to 8; ML_(n) is a lewis acid; wherein B is ##STR24## Y isCH═CH, O, NH, S or Se; D is OR", NR" R' or SR" whereR" is H, alkyl, arylor (CH₂)_(w) OH where w=1 to 8; R" is H, alkyl, aryl or (CH₂)₂ OH wherez=1 to 8; or where R" R"' is derived from a cyclic amine of the formN(CH₂)₁ where I=3-10; and wherein m is 0 to 15; where the asteriskindicates the point of attachment on the acceptor and donor; and B)means for directing at least one incident beam of electromagneticradiation having at least one frequency into said element wherebyelectromagnetic radiation emerging from said element has at least onefrequency which is different from said at least one frequency of saidincident beam of electromagnetic radiation.
 2. A nonlinear opticaldevice according to claim 1 wherein said means for directing saidincident beam of radiation is a laser.
 3. A nonlinear optical deviceaccording to claim 1 wherein R is H or ethyl.
 4. A nonlinear opticaldevice according to claim 1 wherein R' is H or ethyl.
 5. A nonlinearoptical device according to claim 1 wherein R is H or ethyl.
 6. Anonlinear optical device according to claim 1 wherein ML_(n) is (CH₃)₂Zn, (CH₃)₃ A1, (CH₃)₃ Ga, (CH₃)₃ B Cl₃ Al, Cl₃ Ga, and Cl₃ B.
 7. Anonlinear optical device according to claim 1 wherein said elementcomprises a thin film or a crystal.